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Method To Improve Flowability Of Resin Coated Sand - Patent 4996249

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United States Patent: 4996249


































 
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	United States Patent 
	4,996,249



 Johnson
,   et al.

 
February 26, 1991




 Method to improve flowability of resin coated sand



Abstract

A process for improving the flowability of resin coated sand which
     comprises the use of a fluorosurfactant with the mixture of sand and
     resin. Also provided is a resin binder containing a fluorosurfactant and a
     foundry mix comprising foundry sand, a resin binder and a
     fluorosurfactant. The resins used are alkaline phenolic resole resins and
     acid-curable resins.


 
Inventors: 
 Johnson; Calvin K. (Lockport, IL), Cooke; Richard C. (North Riverside, IL), Tse; Kwok-Tuen (Chicago, IL) 
 Assignee:


Acme Resin Corporation
 (Westchester, 
IL)





Appl. No.:
                    
 07/344,132
  
Filed:
                      
  April 27, 1989





  
Current U.S. Class:
  523/144  ; 428/404; 523/145; 524/144; 524/156; 524/165; 524/376
  
Current International Class: 
  B22C 1/22&nbsp(20060101); B22C 1/16&nbsp(20060101); C08K 5/02&nbsp(20060101); C08K 5/00&nbsp(20060101); C08K 005/524&nbsp(); C08K 005/41&nbsp(); C08K 005/06&nbsp(); C08L 061/06&nbsp()
  
Field of Search: 
  
  







 523/144,145,146 428/404 524/144,156,165,376
  

References Cited  [Referenced By]
U.S. Patent Documents
 
 
 
3644274
February 1972
Maurukas

4236569
December 1980
Epstein et al.

4468359
August 1984
Lemon et al.

4474904
October 1984
Lemon et al.

4495316
January 1985
Armbruster



 Foreign Patent Documents
 
 
 
53-130224
Nov., 1978
JP

54-136524
Oct., 1979
JP

582882
Dec., 1977
SU



   Primary Examiner:  Jacobs; Lewis T.


  Attorney, Agent or Firm: Rockey and Rifkin



Claims  

What is claimed is:

1.  A process for improving the flowability of sand coated with a resin binder selected from the group consisting of alkaline phenolic resole resin binders and acid-curable
resin binders which comprises incorporating in the mixture of sand and resin binder fluorosurfactant in an amount from about 0.01 percent to about 5 percent by weight of the resin binder


2.  The process of claim 1 wherein the fluorosurfactant is added to the resin binder before it is coated on the sand.


3.  The process of claim 1 wherein the resin binder is an aqueous alkaline solution of an ester-curable phenolic resole resin.


4.  The process of claim 3 wherein the phenolic resole resin further comprises an ester.


5.  The process of claim 4 wherein the ester comprises triacetin.


6.  The process of claim 1 wherein the resin binder is an acid-curable no bake foundry resin.


7.  The process of claim 6 wherein the acid-curable no bake foundry resin comprises a phenolic resin.


8.  The process of claim 6 wherein the acid-curable no bake foundry resin comprises a furan resin.


9.  The process of claim 6 wherein the sand is also coated with an acid catalyst.


10.  The process of claim 1 wherein the resin binder is an acid-curable hot box foundry resin.


11.  The process of claim 10 wherein the acid-curable hot box resin comprises a phenolic resin.


12.  The process of claim 1 wherein the amount of fluorosurfactant is from about 0.1 percent to about 2 percent by weight of the resin binder.


13.  A foundry mix for preparing foundry cores and molds which comprises a foundry sand, from about 0.5 percent to about 8 percent by weight of the sand of a resin binder selected from the group consisting of alkaline phenolic resole resin
binders and acid-curable resin binders and from about 0.01 percent to about 5 percent by weight of the resin binder of a fluorosurfactant.


14.  The foundry mix of claim 13 wherein the resin binder is an aqueous alkaline solution of an ester-curable phenolic resole resin.


15.  The foundry mix of claim 14 wherein the phenolic resole resin further comprises an ester.


16.  The foundry mix of claim 15 wherein the ester comprises triacetin.


17.  The foundry mix of claim 13 wherein the resin binder is an acid-curable no bake foundry resin.


18.  The foundry mix of claim 17 wherein the acid-curable no bake foundry resin comprises a phenolic resin.


19.  The foundry mix of claim 17 wherein the acid-curable no bake foundry resin comprises a furan resin.


20.  The foundry mix of claim 17 wherein the sand is also coated with an acid catalyst.


21.  The foundry mix of claim 13 wherein the resin binder is an acid-curable hot box foundry resin.


22.  The foundry mix of claim 21 wherein the acid-curable hot box resin comprises a phenolic resin.


23.  The foundry mix of claim 13 wherein the amount of fluorosurfactant is from about 0.1 percent to about 2 percent by weight of the phenolic resole resin.


24.  A binder for foundry cores and molds which comprises a resin binder selected from the group consisting of alkaline phenolic resole resin binders and acid-curable resin binders and from about 0.01 percent to about 5 percent by weight of the
resin binder of a fluorosurfactant.


25.  The binder of claim 24 wherein the resin binder is an aqueous alkaline solution of an ester-curable phenolic resole resin.


26.  The binder of claim 25 wherein the phenolic resole resin further comprises an ester.


27.  The binder of claim 26 wherein the ester comprises triacetin.


28.  The binder of claim 24 wherein the phenolic resole resin binder is an acid-curable no bake foundry resin.


29.  The binder of claim 28 wherein the acid-curable no bake foundry resin comprises a phenolic resin.


30.  The binder of claim 28 wherein the acid-curable no bake foundry resin comprises a furan resin.


31.  The binder of claim 28 wherein the sand is also coated with an acid catalyst.


32.  The binder of claim 24 wherein the resin binder is an acid-curable hot box foundry resin.


33.  The binder of claim 32 wherein the acid-curable hot box resin comprises a phenolic resin.


34.  The binder of claim 24 wherein the fluorosurfactant comprises from about 0.1 percent to about 2 percent by weight of the binder.  Description  

FIELD OF THE INVENTION


This invention relates to resin binders useful for making foundry sand cores and molds and to a method for improving the flowability of sands coated with the resins.


BACKGROUND OF THE INVENTION


Binders or binder systems for foundry cores and molds are well-known.  In the foundry art, cores or molds for making metal castings are normally prepared from a mixture of an aggregate material, such as sand, and a binding amount of a binder or
binder system.  Typically, after the aggregate material and binder have been mixed, the resulting mixture is rammed, blown or otherwise formed to the desired shape or pattern, and then cured with the use of catalysts and/or heat to a solid, cured state.


A variety of different processes for forming molds and cores have been developed in the foundry industry One type of process known as the "hot-box" process requires that the mixture of aggregate material and binder be cured and hardened in a
holding pattern or core box while subjected to heat.  Another type of binder system which does not require heating in order to bring about curing or hardening is known as a "no-bake" process.  A third type of process used for forming molds or cores is
known as the "cold-box" process.  "Cold-box" processes are generally carried out by passing gaseous catalysts or hardeners through molded resin-coated sand at ambient temperatures in order to achieve curing.


Resins cured with acids or acid salts have been used in both the hot box and no bake processes.  Such acid cured resins include both phenolic and furan resins as well as mixtures of these with other resins.  Akaline solutions of phenolic resole
resins have been used as binders in both no bake and cold box processes.  When such alkaline phenolic resole resins are used in the no bake process, they are cured by the addition of a liquid ester hardener.  When the alkaline phenolic resole resin
binders are used in the cold box process, they are cured by means of a gaseous or vaporized ester hardener.


Sands coated with alkaline phenolic resole and acid-curable resins tend to have less flowability than sands coated with certain other binder systems This can adversely affect quality of the foundry cores and molds.  In the case of the cold box
process, higher blow pressures are needed to blow the coated sand into the core boxes and it is more difficult to blow uniformly dense cores.


Now it has been found, in accordance with this invention, that the use of certain surfactants improves the flowability of sands coated with alkaline phenolic resole and acid-curable resin binders.  These sands form cores and molds with smoother
surfaces and sharper edges, as well as with more uniform density.  Such cores and molds give castings of better quality.  This improvement also makes possible the production of cores and molds with more delicate patterns.  Furthermore, when the resin
coated sands of this invention are blown into core boxes, they can be blown at lower pressures resulting in less pattern wear and in less sand being blown out of the vents.  In addition, the cores prepared from these sands are released more readily from
the core boxes.


SUMMARY OF THE INVENTION


In accordance with this invention, there is provided a process for improving the flowability of sand coated with a resin binder selected from the group consisting of alkaline phenolic resole resin binders and acid-curable resin binders.  This
comprises incorporating into the mixture of sand and resin binder fluorosurfactant in an amount from about 0.01 percent to about 5 percent by weight of the resin binder.


Further provided, in accordance with this invention, is a foundry mix for preparing foundry cores and molds which comprises a foundry sand, from about 0.5 percent to about 8 percent by weight of the sand of a resin binder selected from the group
consisting of alkaline phenolic resole resin binders and acid-curable resin binders, and from about 0.01 percent to about 5 percent by weight of the phenolic resole resin of a fluorosurfactant.


Also provided, in accordance with this invention, is a binder for foundry cores and molds which comprises a resin binder selected from the group consisting of alkaline phenolic resole resin binders and acid-curable resin binders, and from about
0.01 percent to about 5 percent by weight of the resin binder of a fluorosurfactant.


DESCRIPTION OF THE PREFERRED EMBODIMENTS


The process of this invention may be employed with various resins used as binders for foundry sand cores and molds.  These include the resins which are cured by acids or acid salts in hot box or no bake processes.  The process of this invention
is particularly useful with the alkaline phenolic resole resin binders which are cured by one or more esters such as methyl formate, triacetin, butyrolactone and the like.


Ester-cured alkaline phenolic resole resin binders may be used in either the no bake or cold box processes.  When they are used in the no bake process, the resin and ester are first coated on the sand.  The coated sand is then placed in a core or
mold box, and the resin is allowed to cure at ambient temperature to give a solid core or mold.  This process and useful esters are described in detail in U.S.  Pat.  No. 4,474,904 (U.S.  Pat.  No. Re.  32,812) which is incorporated herein by reference
in its entirety.


When ester-cured alkaline phenolic resole resin binders are used in the cold box process, foundry sand is coated with the resin.  The resin coated sand is blown into a core box.  Then a gaseous or vaporized ester, such as methyl formate is passed
through the coated sand to cure the resin.  This process is described in detail in U.S.  Pat.  No. 4,468,359 (U.S.  Pat.  No. Re.  32,720) which is also incorporated herein by reference in its entirety.


The acid-cured resin binders which may be used with this invention include a wide range of products made from phenolic resole resins, urea formaldehyde resins, or furfuryl alcohol or its reaction products with formaldehdye or phenol or various
mixtures of the above.  Two commercial types of hot box resins are the phenolic and furan resins.  The phenolic hot box resins are typically a mixture of phenolic resole and urea formaldehyde resin while the furan hot box resins are typically a mixture
of furfuryl alcohol or its reaction products with formaldehyde and urea formaldehyde resin.  Blends of these two types of hot box resins are also possible to yield phenolic-furan hot box resins.


Acid-curable no bake resins include a wide range of products made from phenol, urea, formaldehyde and furfuryl alcohol.  Some no bake resins do not contain urea.  These types include the phenolic resole no bake binders and the furan no bake
binders or blends of phenolic or furan resins.  Many phenolic or furan no bake resins also contain urea formaldehyde resin.


The acid cured hot box resins typically are cured with acid salt catalysts.  Ammonium nitrate and ammonium chloride are often used for this purpose.  Acid cured no bake resins are cured with acids such as toluene sulfonic acid, benzene sulfonic
acid or phosphoric acid.


Any refractory material commonly used to make foundry cores and molds can be used in the composition and process of this invention.  Such refractory material includes silica sands, lake sands, bank sands, zircon sands, chromite sand, olivine sand
and the like.  Also, mixtures of these materials may be used.


The resin binders used in the processes can be employed in the proportions normally used in foundry binder operations.  Normally these are between about 0.5 parts and about 8 parts by weight of the resin binder per 100 parts of the refractory
material.


In the practice of this invention, a fluorosurfactant in an amount from about 0.01 percent to about 5 percent, preferably from about 0.1 percent to about 2 percent by weight of the resin binder is used.  This fluorosurfactant may be mixed with
the resin before it is coated on the sand.  Alternatively, the fluorosurfactant may be added separately before, during or after the coating of the sand with the resin.


The fluorosurfactant used in the practice of this invention may be anionic, nonionic, cationic or amphoteric.  These fluorosurfactants contain one or more fluorocarbon hydrophobic groups attached to an ionic or nonionic hydrophilic group. 
Suitable fluorosurfactants are those available from the DuPont Company under the trade name Zony.RTM.  and the surfactants available from the 3M Corporation having the Fluorad trademark.


It is often the practice in the foundry art to include a variety of additives in the resins used to prepare foundry cores and molds.  These additives include such materials as silanes, deodorizing agents, urea, and the like.  Such additives may
be used in the present process and do not interfere with the improved flowability of the resin coated sands.


The following examples illustrate the invention.  It is to be understood that the examples are illustrative only and do not intend to limit the invention in any way.  In the examples, all parts and percentages are by weight, unless otherwise
indicated. 

EXAMPLE I


WEDRON 530 sand was coated with a mixture of an alkaline phenolic resin and a fluorosurfactant.  The amount of resin used was 1.75 percent by weight of the sand and the amount of fluorosurfactant used was about 3 percent by weight of the phenolic
resole resin.  The alkaline phenolic resole resin used was a commercial resin, BETASET 9511, available from the Acme Resin Corporation, Westchester, Ill.  Four different fluorosurfactants were used.  These were anionic surfactant FC-109, cationic
surfactant FC-135, and nonionic surfactants FC-171 and FC-430.  All of these surfactants are available from the 3M Company, St.  Paul, Minn.  under the trade name Fluorad.  A comparative test was made using sand coated with the resin without the addition
of any fluorosurfactant.


Flowability of the resin coated sands was measured three minutes after resin was added to the sand by the moldability test given in the AFS Mold and Core Test Handbook.  In this procedure, 300 g of the resin coated sand was placed in a Dietert
lab moldability and work life tester equipped with an eight-mesh cylindrical screen.  The sand mix was riddled through the screen for ten seconds.  Moldability index was calculated as the percentage of sand which passed through the screen.  Results of
the test given in Table I show that the sand coated with resin containing the fluorosurfactant had a much higher moldability index and consequently much greater flowability than sand coated with the resin only.


 TABLE I  ______________________________________ Moldability of Sand Coated with  BETASET 9511 and Fluorosurfactants  Fluorosurfactants Moldability Index  ______________________________________ None (Comparative Test)  71.5  FC-109 (3.3%) 92.2 
FC-135 (3.0%) 92.6  FC-171 (3.1%) 88.0  FC-430 (3.1%) 78.3  ______________________________________


EXAMPLE II


The general procedure of Example I was followed except that varying amounts of the fluorosurfactants FC-109 and FC-135 were added to the sand.  The results given in Table II show that sand coated with the phenolic resin containing reduced amounts
of fluorosurfactant still showed much improved flowability over the comparative test which contained no fluorosurfactant.


 TABLE II  ______________________________________ Moldability of Sand Coated With  BETASET 9511 and Fluorosurfactants  Moldability Index  % Fluorosurfactant FC-109 FC-135  ______________________________________ 0 (Comparative Test)  71.5 71.5 
0.5 83.0 --  0.75 84.9 88.8  1.0 86.6 --  1.5 87.3 92.0  3.0 -- 92.6  3.3 92.2 --  ______________________________________


Sands coated with the BETASET 9511 resin containing 1 percent fluorosurfactant FC-109 were tested making standard AFS (dog bone) tensile cores.  Test cores were prepared by blowing the mixture at 80 pounds per square inch air pressure into a
Redford Laboratory three cavity cold box machine.  The cores were cured by gassing with a 70:30 mixture of methyl formate and air for seven seconds.  The core box was opened after ten seconds and the cores were removed.  Release characteristics of the
cured cores was noted.  A series of cores was prepared without cleaning the core box.  The same procedure was followed using sand coated with the resole resin BETASET 9511 to which no fluorosurfactant had been added.  It was increasingly more difficult
to remove each subsequent set of cores when no surfactant was present.  However, when the surfactant was present, subsequent sets of cores were released more readily from the core box.  This improved release of cores is an additional advantage observed
when the process of this invention is followed.


EXAMPLE III


The general procedure of Example I was followed except that the phenolic resole resin employed was AlpHASET 9010 resin, available from the Acme Resin Corporation, Westchester, Ill.  Sand was coated using 1.5 percent by weight of the resin and
0.38 percent by weight of the ester hardener, triacetin.  The resin contained 1 percent of one of the following fluorosurfactants available from E. I. DuPont de Nemours Co., Wilmington, Del.: the anionic surfactant FSA, the cationic surfactant FSC, the
amphoteric surfactant FSK, and the nonionic surfactant FSN.  The results of the moldability tests are given in Table III.  They demonstrate that these fluorosurfactants all improve the flowability of sand coated with the ester curable alkaline phenolic
resole resin.


 TABLE III  ______________________________________ Moldability of Sand Coated with  ALpHASET 9010 and Fluorosurfactants  Fluorosurfactant Moldability Index  ______________________________________ FSA 94.6  FSC 91.6  FSK 93.9  FSN 91.4  None
(comparative test)  84.1  ______________________________________


EXAMPLE IV


The general procedure of Example I was followed except that the resin coated on the sand was either a hot box resin or an acid-cured no bake resin.  The hot box resin employed was Resin 745 PL, a phenolic resole resin also containing
urea-formaldehyde, available from the Acme Resin Corporation, Westchester, Ill.  Sand was first coated with 0.45 percent by weight of the acid salt catalyst 45 MRlBS available from the Acme Resin Corporation, Westchester, Ill.  The mixture was stirred
for one minute and then 1.5% by weight of resin was added and the mixture was stirred for another minute.  The resin contained 1 percent by weight of a fluorosurfactant.  The resin coated sand was then tested for flowability using the moldability index
test.


A phenolic no bake Resin 975 available from the Acme Resin Corporation, Westchester, Ill.  containing 1 percent by weight of various fluorosurfactants was tested in a similar manner.  In this case, 0.4% by weight of the acidic catalyst 91D (Acme
Resin Corporation) was first coated on the sand and then the resin containing the fluorosurfactant was added to the sand.


A number of different fluorosurfactants available from the DuPont Company and the 3M Company were employed in these tests.  Results of the tests given in Table IV show that many fluorosurfactants are suitable for use in the process of this
invention.


 TABLE IV  ______________________________________ Moldability of Sand Coated With Hot Box and No  Bake Resins and Fluorosurfactants  Moldability Index  Fluorosurfactants  Hot Box Resin  No Bake Resin  ______________________________________
ANIONICS  DuPont FSJ 69.1 (a)  DuPont FSA 76.1 70.3  DuPont FSE 67.9 58.3  DuPont FSP 67.0 68.0  DuPont TBS 61.4 63.0  3M FC-109 71.1 71.7  3M FC-120 75.2 69.0  CATIONIC  DuPont FSC 78.4 73.5  3M FC-135 76.3 88.3  AMPHOTERIC  DuPont FSK 70.3 75.7 
NONIONIC  DuPont FSN 61.8 69.3  DuPont FSO 74.9 70.7  3M FC-170C 73.3 74.6  3M FC-171 69.6 78.6  3M FC-430 75.5 64.7  3M FC-431 68.9 63.0  COMPARATIVE TEST  None 59.4 54.4  ______________________________________ (a) Resin and surfactant were incompatible


EXAMPLE V


The general procedure of Example IV was followed except that the resin coated on the sand was a furan no bake resin.  The resin employed was Furan No Bake Resin 935, available from the Acme Resin corporation, Westchester, Ill.  Sand was first
coated with 0.45 percent by weight of the acid catalyst 94A, also available from the Acme Resin Corporation.  Then, 1.5 percent by weight of resin containing 1 percent of a fluorosurfactant was added.  The fluorosurfactants used were the DuPont
fluorosurfactants used in Example III.  Results of the tests given in Table V show that fluorosurfactants improve the flowability of sand coated with an acid curable no bake furan resin.


 TABLE V  ______________________________________ Moldability of Sand Coated With a Furan No Bake Resin  Fluorosurfactants  Moldability Index  ______________________________________ FSA 61.6  FSC 63.1  FSK 64.1  None (Comparative test)  59.2 
______________________________________


Thus, it is apparent that there has been provided, in accordance with this invention, a method for improving the flowability of resin coated sand that fully satisfies the objects, aims and advantages set forth above.  While the invention has been
described in conjunction with specific embodiments thereof, it is evident that many alternatives, modifications and variations will be apparent to those skilled in the art in light of the foregoing description.  Accordingly, it is intended to include all
such alternatives, modifications and variations as set forth within the spirit and broad scope of the appended claims.


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DOCUMENT INFO
Description: This invention relates to resin binders useful for making foundry sand cores and molds and to a method for improving the flowability of sands coated with the resins.BACKGROUND OF THE INVENTIONBinders or binder systems for foundry cores and molds are well-known. In the foundry art, cores or molds for making metal castings are normally prepared from a mixture of an aggregate material, such as sand, and a binding amount of a binder orbinder system. Typically, after the aggregate material and binder have been mixed, the resulting mixture is rammed, blown or otherwise formed to the desired shape or pattern, and then cured with the use of catalysts and/or heat to a solid, cured state.A variety of different processes for forming molds and cores have been developed in the foundry industry One type of process known as the "hot-box" process requires that the mixture of aggregate material and binder be cured and hardened in aholding pattern or core box while subjected to heat. Another type of binder system which does not require heating in order to bring about curing or hardening is known as a "no-bake" process. A third type of process used for forming molds or cores isknown as the "cold-box" process. "Cold-box" processes are generally carried out by passing gaseous catalysts or hardeners through molded resin-coated sand at ambient temperatures in order to achieve curing.Resins cured with acids or acid salts have been used in both the hot box and no bake processes. Such acid cured resins include both phenolic and furan resins as well as mixtures of these with other resins. Akaline solutions of phenolic resoleresins have been used as binders in both no bake and cold box processes. When such alkaline phenolic resole resins are used in the no bake process, they are cured by the addition of a liquid ester hardener. When the alkaline phenolic resole resinbinders are used in the cold box process, they are cured by means of a gaseous or vaporized ester hardener.Sands coated